• Title/Summary/Keyword: 31P NMR

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Synthesis and Configuration Analysis of Diastereomers of 5'-O-(2'-Deoxycytidyl)-3'-O-Thymidyl Phosphorothioate

  • Mun, Byeong Jo;Jeong, Hyeon Ju;Kim, Sang Guk;Kim, Nam Hui
    • Bulletin of the Korean Chemical Society
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    • v.17 no.1
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    • pp.24-28
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    • 1996
  • A procedure is described for the synthesis of the title compound via phosphotriester intermediates. The preparation of $R_p$ and $S_p$ diastereomeric dinucleotide of d[Cp(S)T] was performed by the condensation of the protected deoxycytidine, the protected thymidine, 2,5-dichlorophenylphosphorodichloridothioate and 1-hydroxybenzotriazole in THF. Their designation of configuration at phosphorus as $R_p$ and $S_p$ follows from anaylsis of ${31}^P$ NMR spectroscopy and reverse-phase HPLC and the stereospecificity in the hydrolysis catalyzed by Nuclease S1 and snake venom phosphodiesterase. Diastereomerically pure $R_p$ and $S_p$ d[Cp(S)T] were utilized to synthesize oligonucleotides containing the XhoI recognition sequence with a phosphorothioate group at the cleavage site.

The Effect of Ginkgo Biloba Extract on Hypoxic Fraction of C3H Mouse Fibrosarcoma (Ginkgo Biloba Extract가 C3H 마우스 섬유육종의 저산소세포 분획에 미치는 영향)

  • Cho Chul Koo;Yi Chun Ja;Ha Sung Whan;Park Charn Il
    • Radiation Oncology Journal
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    • v.13 no.3
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    • pp.205-214
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    • 1995
  • Purpose : To investigate the effect of Ginkgo biloba extract (GBE) on hypoxic cell fraction and metabolic status in fibrosarcoma (FSa II) of C3H mouse. Materials and Methods : Fibrosarcoma (FSa II) 6 mm in diameter, growing in the right hindleg muscle of C3H mouse was used for estimation of hypoxic cell fraction using comparison of $TCD_{50}$. Radiation was given one hour after administration of GBE (100 mg/kg. i.p.) with or without priming dose of GBE (100 mg/kg, i.p.) given 24 hours earlier. Radiation was also given under air breathing condition or clamp hypoxia without GBE as controls. $^{31}p$ NMR spectroscopy was performed before and one hour after administration of GBE with or without priming dose of GBE. Results : $TCD_{50/120's}$ were 81.7 (77.7-86.0) Gy when irradiated under clamped hypoxia 69.6 (66.8-72.5) Gy under air breathing condition. 67.5 (64.1-71.1) Gy with a single dose of GBE (100 mg/kg) given one hour before irradiation, and 62.2 (59.1-65.5) Gy with two doses of GBE given at 25 hours and one hour before irradiation. The hypoxic cell fractions, estimated from $TCD_{50/120's}$, were $10.6{\%}$ under air breathing condition, $7.2{\%}$ after a single dose of GBE, and $2.7{\%}$ after two doses of GBE. The results of $^{31}P$ NMR spectroscopy were as follow. PCr/Pi ratio was $0.27{\pm}0.04$ and $0.40{\pm}0.04$ before and one hour after a single dose of GBE (p<0.05), respectively, without priming dose and $0.30{\pm}0.02$ and $0.71{\pm}0.04$, respectively, with priming dose (p<0.01). These findings indicate that the metabolic status is slightly improved after a single dose and markedly after repeated administrations. Conclusion : GBE decreases the hypoxic cell fraction and imprvoes the meta bolic status of tumor, probably by increasing the blood flow and delivery of oxygen and nutrients, resulting in increased radiosensitivity of tumor.

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A Study on Synthesis and Wear Characteristics of Mo-DTP as Lubricant Additive (윤활유 첨가제로써 Mo-DTP의 합성과 마찰마모특성에 관한 연구)

  • 김종호;강석춘;정근우;조원오;한두희
    • Tribology and Lubricants
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    • v.5 no.1
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    • pp.57-63
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    • 1989
  • The soluble Mo-DTP compounds as lubricant additives for reducing friction and wear, increasing loadcarrying capacity, and as antioxidants is very important as a new additive developed in these day. The method of the compounds are described and the composition is analyzed with $^{31}$P NMR spectrometer. The wear test is conducted with 4-ball machine and the debris are analyzed by ferrography. Also the tribological performance of Mo-DTP compounds are compared with Moly Van L and Zn-DTP.

A Potential Flame-retardant by Intumescence. Melaminium 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-4-methoxy-sulfates

  • 김진규;조양하;정옥상;손윤수
    • Bulletin of the Korean Chemical Society
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    • v.16 no.1
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    • pp.62-65
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    • 1995
  • New compounds of melaminium 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-4-methoxy-sulfate have been synthesized and characterized by means of chemical analysis, 1H, 13C, and 31P NMR, and IR spectroscopies. When the compounds are subjected to an open flame, they foam without melting to produce a light char with about 50 times volume of the initial compounds. The evaluation of these flame-retardants proves to be efficient for polypropylene. Thermogravimetric analysis discloses that the compounds are also thermally stable for compounding into polypropylene without decomposition.

Ab Initio Study of the Conformations of Tetramethoxycalix[4]arenes

  • Choe, Jong-In;Lee, Sang-Hyun;Oh, Dong-Suk
    • Bulletin of the Korean Chemical Society
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    • v.25 no.1
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    • pp.55-58
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    • 2004
  • In this study we have performed ab initio computer simulations to investigate the conformational characteristics of the tetramethoxycalix[4]arenes (1 and 2). The structures of four types (cone, partial cone, 1,2-alternate, and 1,3-alternate) of conformers for each compound have been optimized using ab initio RHF/6-31G and 6-31$G^{**}$ methods. General trends in relative stabilities of tetramethyl ether derivatives of calix[4]arene 1 and p-tert-butylcalix[4]arene 2 are similar and decrease in following order: partial cone (most stable) > cone > 1,3-alternate > 1,2-alternate. The calculated results of the most stable conformation of partial cone structure agree with the reported NMR experimental observations.

Cytotoxic Compounds from the Flowers of Paulownia coreana (오동나무꽃의 항암성분)

  • Oh, Joa-Sub;Zee, Ok-Pyo;Moon, Hyung-In
    • Korean Journal of Pharmacognosy
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    • v.31 no.4
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    • pp.449-454
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    • 2000
  • In search for plant-derived cytotoxic compounds, it was found that the $CHCl_3$ and EtOAC extracts obtained from the flowers of Paulownia coreana Uyeki (Scrophulariaceae) exhibited significant cytotoxic activity against human tumor cell lines, A549, SK-OV-3, SK-MEL-2, XF498, and HCT15. Activity-guided fractionation on the basis of the inhibitory activity against the growth of human tumor cell lines, in vitro, and repeated column chromatography afforded several cytotoxic compounds from P. coreana. The structures and stereochemistry of these compounds were established, on the basis of analysis of spectra including IR, UV, EI-MS, $^{1}H-NMR,\;^{13}C-NMR$ and some chemical transformations, as Compound PCCl $(2-hydroxy-4(15),11(13)-eudesmadien-8{\beta},12-olide)$, Compound $PCC2(2,3-dihydro-4-hydroxy-1(15),11(13)-xanthadien-8{\beta},12-olide)$, Compound PCE1 (chrysophanol), Compound PCE2 (emodin), Compound PCE3 (physcion). Cytotoxic activity of compounds obtained from P. coreana. on five tumor cells lines was evaluated by procedure of SRB methods.

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Synthesis and Configurational Analysis of Diastereomers of $5^{\prime}-O-(2^{\prime}-Deoxyadenosyl)-3^{\prime}-O-(2^{\prime}$-deoxyadenosyl)-Phosphorothioate

  • Byung Jo Moon;Kyung Lan Huh;Sang Kook Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.1
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    • pp.52-55
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    • 1993
  • A procedure is described for the synthesis of the title compound via phosphotriester intermediates. The preparation of $R_p\;and\;S_p$ diastereomeric dinucleotide of d[Ap(S)A] was performed by the condensation of protected deoxyadenosine, 2,5-dichlorophenylphosphorodichloridothioate and 1-hydroxybenzotriazole in THF. Their designation of configuration at phosphorus as $R_p\;and\;S_p$ follows from analysis of $^{31}P$-NMR spectroscopy and reversed-phase HPLC and the stereospecificity in the hydrolysis catalyzed by nuclease Pl.

The Effect of Nuclear Overhauser Enhancement in Liver and Heart $^{31}P$ NMR Spectra Localized by 2D Chemical Shift Technique (이차원 화학변위 기법을 이용한 간 및 심장 $^{31}P$ 자기공명분광에서의 Nuclear Overhauser 효과에 대한 연구)

  • Ryeom Hun-Kyu;Lee Jongmin;Kim Yong-Sun;Lee Sang-Kwon;Suh Kyung-Jin;Bae Sung-Jin;Chang Yongmin
    • Investigative Magnetic Resonance Imaging
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    • v.8 no.2
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    • pp.94-99
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    • 2004
  • Purpose : To investigate the signal enhancement ratio by NOE effect on in vivo $^{31}P$ MRS in human heart muscle and liver. we also evaluated the enhancement ratios of different phosphorus metabolites, which are important in 31P MRS for each organ. Materials and Methods : Ten normal subjects (M:F = 8:2, age range = 24-32 yrs) were included for in vivo $^{31}P$ MRS measurements on a 1.5 T whole-body MRI/MRS system using $^1H-^{31}P$ dual tuned surface coil. Two-dimensional Chemical Shift Imaging (2D CSI) pulse sequence for $^{31}P$ MRS was employed in all $^{31}P$ MRS measurements. First, $^{31}P$ MRS performed without NOE effect and then the same 2D CSI data acquisitions were repeated with NOE effect. After postprocessing the MRS raw data in the time domain, the signal enhancements in percent were estimated from the major metabolites. Results : The calculated NOE enhancement for liver $^{31}P$ MRS were $\alpha-ATP\;(7\%),\;\beta-ATP\;(9\%),\;\gamma-ATP\;(17\%),\;Pi\;(1\%),\;PDE\;(19\%)$ and $PME\;(31\%)$. Because there is no creatine kinase activity in liver, PCr signal is absent. For cardiac $^{31}P$ MRS, whole body coil gave better scout images and thus better localization than surface coil. In $^{31}P$cardiac multi-voxel spectra, DPG signal increased from left to right according to the amount of blood included. The calculated enhancement for cardiac $^{31}P$ MRS were : $\alpha-ATP\;(12\%),\;\beta-ATP\;(19\%),\;\gamma-ATP\;(30\%),\;PCr\;(34\%),\;Pi\;(20\%),\;(PDE)\;(51\%),\;and\;DPG\;(72\%)$. Conclusion : Our results revealed that the NOE effect was more pronounced in heart muscle than in liver with different coupling to 1H spin system and thus different heteronuclear cross-relaxation.

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Photoluminescence analysis of Lewis base coordinate europium(III) β-diketonate complex (유로퓸(III) β-디케토네이트 착물의 루이스 염기 배위에 따른 발광 특성 분석)

  • Sung-Hwan, Lee;Gyu-Hwan, Lee
    • Analytical Science and Technology
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    • v.28 no.3
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    • pp.204-211
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    • 2015
  • Lanthanide complexes have attracted much attention because of their unique light emitting property. The light-emitting efficiencies of europium β-diketonate complexes were compared with those of complexes coordinated by the ligands of amines or phosphine oxides. The results demonstrated that the complexes that were coordinated by phosphine oxides had higher light-conversion performance than those coordinated by amines. The highest light-emitting efficiency was observed when the ligand of trioctylphosphine oxide was coordinated. In order to determine the coordination equivalency of trioctylphosphine oxide in the above complexes, 31P-NMR and their photoluminescence spectra were measured. The findings showed that the europium β-diketonate complex had one or two coordination equivalencies of trioctylphosphine oxide according to the steric hindrance of its original ligand.

Synthesis and Characterization of Two Different 1,3-Dithiole-2-thiones as the Precursors of TTF Donor Molecule (TTF 주게분자의 전구체로서 두 가지 다른 1,3-Dithiole-2-thione 화합물의 합성 및 특성화)

  • Kim, Young-Youn;Lee, Ha-Jin;Namgoong, Sung Keon;Hong, Jong-Ki;Noh, Dong-Youn
    • Journal of the Korean Chemical Society
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    • v.44 no.6
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    • pp.513-517
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    • 2000
  • As a precursor of tetrathiafulvalene (TTF) derivative, 5,6-dimethyl-1,3-dithiolo[4,5-b][1,4]dithiin-2-thione (compound 3) was synthesized by the unusual Lawesson's reaction. Depending upon the substituents such as dimethyl and diphenyl groups, two different products containing 1,4-dithiin and thiophene moieties, respectively, were obtained and characterized by $^{13}C$ NMR and high-resolution electron impact (HREI) mass spectroscopy. The formation of 3 was further characterized by X-ray structure analysis. Crystallographic data for 3: triclinic, space group P1, a=4.145(2)$\AA$, b=10.600(2)$\AA$, c=12.279(2)$\AA$, $\alpha$=71.440(10)$^{\circ}$, $\beta$=84.30(2)$^{\circ}$, $\gamma$=87.31(2)$^{\circ}$, Z=2 and R(wR$_2$)=0.0559(0.1416). The formation mechanism of two products was suggested and compared each other.

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